Summary

Carboxybetaine viscoelastic surfactants have been applied in acid diversion and fracturing treatments in which high temperatures and low pH are usually involved. These surfactants are subjected to hydrolysis under such conditions because of the existence of a peptide group (-CO-NH-) in their molecules, leading to changes in the rheological properties of the acid. The objective of this paper is to study the impact of hydrolysis at high temperatures on the apparent viscosity of carboxybetaine viscoelastic surfactant-based acids, and propose the mechanism of viscosity changes by molecular dynamics (MD) simulations.

Surfactant-acid solutions with different compositions (surfactant concentration varied from 4 to 8 wt%) were incubated at 190°F for 1 to 6 hours. Solutions were then partially spent by CaCO3 until the sample pH was 4.5, and the apparent viscosity was measured using a high-temperature/high-pressure (HT/HP) viscometer. To understand the mechanism for viscosity changes on the molecular level, MD simulations were carried out on spent surfactant-acid aqueous systems using the Materials Studio 5.0 Package.

It was found that short-time hydrolysis at high temperatures (for example, 1 to 2 hours at 190°F) led to a significant increase in surfactant-acid viscosity. However, after incubation for 3 hours, phase separation occurred and the acid lost its viscosity. Simulation results showed that viscosity changes of amido-carboxybetaine surfactant acid by hydrolysis at high temperatures may be caused by different micellar structures formed by carboxybetaine and fatty acid soap, its hydrolysis product. The optimum molar ratio of amido-carboxybetaine and fatty acid soap to form worm-like micelles was found to be nearly 3:1 from our simulations.

Our results indicate that hydrolysis at high temperatures has a great impact on surfactant-acid rheological properties. Short time viscosity build-up and effective gel breakdown can be achieved if surfactant-acid treatments are carefully designed; otherwise, unexpected viscosity reduction and phase separation may occur, which will affect the outcome of acid treatments.